Phosphoroamidothioates

ABSTRACT

WHEREIN R1 to R6 are as defined above. The compounds are highly active insecticides, with low mammalian toxicity.   WITH A PHOSPHOROAMIDOTHIOATE COMPOUND OF THE FORMULA   WHEREIN R1 and R2 individually are alkyl or alkenyl; R4 is hydrogen, alkyl or haloalkyl; R3 and R5 are hydrogen or alkyl and R6 is alkyl, haloalkyl, aryl, alkoxy, aryloxy, aryloxy, alkylthio, or amino are produced by the acid-catalyzed condensation of a 1,3-dicarbonyl compound of the formula   Compounds of the formula

United States Patent [1 1 Freenor [451 May 6,1975

[ PHOSPHOROAMIDOTHIOATES [75] inventor: Francis J. Freenor, Richmond,

Calif.

[73] Assignee: Chevron Research Company, San

Francisco, Calif.

[22] Filed: Sept. 6, 1973 [21] Appl. No: 394,872

[52] US. Cl. 260/946; 260/941; 260/943;

260/968; 424/211; 424/212; 424/214 [51] Int. Cl. A01n 9/36; C07f 9/24 [58] Field of Search 260/946 [56] References Cited UNITED STATES PATENTS 3,113,958 12/1963 Miller et al. 260/946 X Primary ExaminerLorraine A. Weinber'ger Assistant Examiner-Richard L. Raymond Attorney, Agent, or FirmG. F. Magedburger; John Stoner, Jr.; Raymond Owyang [57] ABSTRACT Compounds of the formula with a phosphoroamidothioate compound of the formula wherein R to R are as defined above. The compounds are highly active insecticides, with low mammalian toxicity.

10 Claims, N0 Drawings PHOSPHOROAMIDOTHIOATES BACKGROUND OF THE INVENTION US. Pat. Nos. 3,676,555 and 3,689,604 of G. Schrader et a1. disclose insecticidal O,S-dialkylphosphoroamidothiotes. US. Pat. Nos. 3,649,723 and 3,716,600 of P. S. Magce disclose O-alkyl-S- unsaturated hydrocarbyl-(N-acyllphosphoroamidothioates.

German application No. 2,116,690, published Oct. 19, 1972, of Farbenfabriken Bayer AG discloses insecticidal O,S-dialkyl-Nalkoxymethylene-(di)thiophosphoramidic acids. German application No. 2,118,469, published Oct. 26, 1972, of Farbenfabriken Bayer AG discloses N-(dimethylaminomethylene)thiolo(thiono)- phosphoric acid ester imides.

DESCRIPTION OF THE INVENTION The insecticidal compounds of the invention are represented by the formula (I) wherein R is lower alkyl of 1 to 6 carbon atoms or lower alkenyl of 3 to 6 carbon atoms;

R is lower alkyl of 1 to 6 carbon atoms or lower alkenyl of 3 to 6 carbon atoms;

R is hydrogen or lower alkyl of l to 6 carbon atoms;

R is hydrogen, lower alkyl of l to 6 carbon atoms,

or lower haloalkyl of l to 6 carbon atoms and l to 3 halogens of atomic number 9 to 35; R is hydrogen or lower alkyl of l to 6 carbon atoms; R lower alkyl of l to 6 carbon atoms, lower haloadlkyl of l to 6 carbon atoms and l to 3 halogens of atomic number 9 to 35, lower alkoxy of 1 to 6 carbon atoms, lower alkylthio of 1 to 6 carbon atoms, phenyl, phenyl substituted with l to 2 alkyl of 1 to 4 carbons, fluorine, chlorine or bromine, phenoxy, phenoxy substituted with 1 to 2 alkyl of 1 to 4 carbon atoms, fluorine, chlorine or bromine, amino N-lower alkylamino of 2 to 7 carbon atoms, N,N- di-lower alkylamino of 3 to 10 carbon atoms, N- phenylamino or N-lower alkylphenylamino of 7 to 10 carbon atoms, with the proviso that two alkyl R and R groups may be joined to form a 5 or 6-membered carbocyclic ring (e.g., R and R are divalent alkylene groups such as dimethylene or trimethylene).

Additional insecticidal compounds of the invention are those wherein R or R are aryl, i.e., phenyl, aralkyl or alkaryl of 7 to 10 carbon atoms optionally substituted with up to 2 groups selected from fluorine, chlorine, bromine, alkoxy of 1 to 4 carbon atoms or nitro, and R, R, R and R are as defined above. Still other insecticidal compounds of the invention are those wherein R is monocyclic aralkyl, alkaryl, aralkoxy, or alkaryloxy of 7 to 10 carbon atoms optionally substituted with up to 2 groups selected from fluorine, ch10 rine, bromine, alkoxy of l to 4 carbon atoms or nitro, and R, R R R and R are as defined above.

The preferred compounds of the invention are those wherein R is alkoxy and R', R R, R and R are as defined above. The particularly preferred compounds of the invention are those wherein R is methoxy or ethoxy and R, R and R are alkyl of 1 to 6 carbon atoms, R and R are hydrogen.

The compounds of the invention are prepared by the acid-catalyzed condensation of a Lil-dicarbonylcontaining compound and a phosphoroamidothioate compound, as depicted in the following equation (1 p-un RC-CIICR6 I I R 3 R3 12 (II) (III) (1) R 0 0 R o (I I II P-u-c=c-c-R 11 0 l l R25 R R5 wherein R, R R R", R and R have the same significance as previously defined.

The reaction depicted in equation (1) is conducted in the presence of a catalytic amount of a strong acid. Suitable strong acids include inorganic acids such as sulfuric acid, halogen acids e.g., hydrochloric acid, phosphoric acid, etc. and organic acids such as arylsulfonic acids e.g., p-toluenesulfonic acid and naphthylenesulfonic acid. The phosphoroamidothioate reactant (11) and the dicarbonyl reactant (III) generally are contacted in molar ratios of 1:2 to 2:], although substantially equimolar ratios are preferred. The reaction is conducted in the liquid phase in inert solvents such as aromatic hydrocarbons e.g., benzene, toluene, xylene, etc. and alkanes e.g., hexane, cyclohexane, isooctane, decane, etc. Suitable reaction temperatures vary from about 50 to C. The product (I) is isolated and purified by conventional procedures such as filtration, extraction, chromatography.

Preparation of the compounds of the invention is illustrated by the following examples.

EXAMPLES Example 1 Preparation of O,S-dimethyl-N-(3- ketopent-2-en-2y1)phosphoroamidothioate cn o 0 C11 0 llIlC=Cl1-C-Cll A solution of 12.65 g (0.09 mol) O,S-dimethylphosphoroamidothioate, 9 g (0.09 mol) acetylacetone, 5 drops concentrated sulfuric acid and 300 ml benzene was heated under reflux for 4 hours in a flask equipped with a Dean-Stark trap. The benzene/water in the Dean-Stark trap was discarded. The reaction mixture was then evaporated to give the product as a yellow oil. Thin-layer chromatography showed the product to be substantially homogeneous. The infrared spectrum of the product showed a,B-unsaturated carbonyl absorption at 6.1 Elemental analysis showed: %S, calc. 14.38, found 14.08; %P, calc. 13.85, found 13.22.

Example 2 Preparation of O,S-dimethyl-N-[1-(N, N '-diethylcarbamyl) propl -en-2-yl lphosphoroamidothioate A solution of 7.58 g (0.054 mol) O,S-dimethy1phosphoroamidothioate. 8.44 g (0.054 mol) 1-(N,N-diethylcarbamyl)-2-propanone, 0.1 g p-toluenesulfonic acid and 500 ml benzene was heated 6 hours under reflux in a flask equipped with a Dean-Stark trap. Three drops of concentrated sulfuric acid were added to the flask and the reaction mixture was heated under reflux an additional 2 hours. The reaction mixture was evaporated to give the product as a yellow oil. The infrared spectrum of the product showed a,B-unsaturated carbonyl absorption at 6.111.. Elemental analysis showed: %S, calc. 11.45; found 10.88.

Example 3 Preparation of O,S-dimethyl-N-[ (carbo-t-butoxy)- prop-l-en-2-yl]phosphoroamidothioate A solution of 7.6 g (0.054 mol) O,S-dimethylphosphoroamidothioate, 8.5 g (0.054 mol) l-carbo-tbutoxypropanZ-one, 0.1 g p-toluenesulfonic acid and 500 ml benzene was heated under reflux for 4 hours in a flask equipped a Dean-Stark trap. Analysis of the reaction mixture by thin-layer chromatography showed small amounts of unreacted l-carbo-t-butoxypropan2- one. Attempts to obtain additional conversion of the l-carbo-t-butoxypropan2-one by additional heating under reflux with a small amount of concentrated sulfuric acid did not significantly reduce the amount of the l-carbo-t-butoxypropan2-one. The reaction mixture was then evaporated to give an oil. The oil was chromatographed on silica gel (benzene eluant) to give the product as a yellow oil. The yellow oil was crystallized from hexane to give the product as a white solid. mp. 6869c. The infrared spectrum of the product showed B-unsaturated carbonyl absorption at 6.05p.. Elemental analysis showed: 7:8, calc. 11.38, found 11.22; %P calc. 11.02, found 10.78. The LD (rats) of the product was 106-124 mg/kg.

Example 4 Preparation of O,S-dimethyl-N-[1-(N'- phenylcarbamylyprop-l-en-2-y1]phosphoroamidothioate This compound was prepared by a procedure similar to that of Examples l-4 from 0.07 mol O,S- dimethylphosphoroamidothioate and 0.14 mol l-carbethoxypropan-2-one. The compound was an oil which showed a,[3-unsaturated carbonyl absorption at 6.0,u. Elemental analysis showed: %S, calc. 12.7, found 13.0.

Example 6 Preparation of O.S-dimethyl-N-(3- ketocyclohexl -enyl )phosphoroamidothioate CH O CH CH 5 CHC This compound was prepared by a procedure similar to that of Examples 14 from 0.077 mol O.S- dimethylphosphoroamidothioate and 0.077 mol 1,3- cyclohexanedione. The compound was a lowmelting solid having a,B-unsaturated carbonyl absorption at 6.2a. Elemental analysis showed: %S, calc. 13.6; found 12.8.

Example 7 Preparation of 0,S-dimethyl-N-( benzoylpropl -en-2-yl )phosphoroam idothioate This compound was prepared by a procedure similar to that of Examples l-4 from 0.063 mol 0,5- dimethylphosphoroamidothioate and 0.065 mol l-benzoylpropan-Z-one. The compound was a yellow oil having afi-unsaturated carbonyl absorption at 6.2. Elemental analysis showed: %S, calc. 11.2; found 12.1. Example 8 Preparation of O,S-dimethyl-N-( carbomethoxypropl -en-2-yl )phosphoroamidothioate This compound was prepared by a procedure similar to that of Examples l4 from 0.075 mol 0,5- dimethylphosphoroamidothioate and 0.077 mol l-carbomethoxypropan-2-one. The compound was a yellow oil having a,B-unsaturated carbonyl absorption 5 at 6.0u. Elemental analysis showed: 708, calc. 13.4, found 12.8.

The phosphoroamidothioate reactant employed in Examples 1-8 may be suitably replaced by the compounds tabulated in Table 1. Similarly, the dicarbonyl 5 reactants employed in Examples l8 may be suitably replaced by the compounds tabulated in Table H. In

TABLE I No. Com ound Table II, 4a represents phenyl. By way of Illustration, p with reference to Tables I and II, the reaction of com- 8.2gihfixylghusfihora iigmgiome la yp osp oramm 0! late pound Nos, b and 3 WI" produce a compound of the 10 c oypmpyhsanylphosphommidothinute formula d O-allyl-S-methylphosphoramidothioate e O-phenyl-S-methylphosphoramidolhioate f O-ethyl-S-p-tolylphosphoramidothioate g O-methyl-S-benzylphosphoramidothioate h o-al|yl-S-p-chlorobenzylphosphoramidothioate CH =CllCll O O O 15 i 0-2,4-dichlorophenyl-S-methylphosphorou n umidothioate P-NHCH=CH (.'Cl[ 3 j O-phenyl-S-p-bromophenylphosphoramidw l0 thioate 2= 2 K O-butyl-S-(2-methyl-4'fluorophenyhphosphnramidothioate l O,S-diethyl-N-methylphosphoramidothioate m O.S-diallyl-N-isopropylphosphoramidothioate 20 n O-allyl-S-phenyl-N-elhylphosphoramidothioate 0 O-P-nilmhenzyl-S-isopropyl-N-methylphosand the reaction of compound Nos. n and 4 ml! pro phmoamidothioam duce EABLE II No Compound E10 Compound l I II II 1 c n ccn cc n l5 F CCCH CCF II II II II 2 (1'1C5H 1)CCll CClI l6 BrzcllccflzccliBrz O O O 3 lieca ccu l7 L M 0 o 0 0 4 c emical; 1B J 6911260? 0 0 l9 ca ccu eo (m-cn 5 c n ecn eo (n-C EI o 0 o 21 C ec en (c11 7 checu t l (p-NO M 0 o 0 22 0x 501 611 (c11 1 2 8 CH ECH EI (0-cu 4n o o O o o 10 ci ecll ecn (p-Brda) 24 13 ClCH CCH CSClI UTILITY The compounds prepared in Examples [-8 were tested as follows to illustrate their insectional activity. Test results are reported in Table lll.

table powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.

Wettable powders are in the form of finely divided TBSt Procedures particles which disperse readily in water or other dis- Cabbage looper (Trichoplusia ni): An acetone solupersam' These compositions normany i l Q tion of the candidate toxicant containing a small 5 80% f and the rest "l mammal which amount of nonionic emulsifier was diluted with water eludes d'spersmg agents emulslfymg flgemsi and w to 500 ppm. Cabbage leaf sections were dipped in the agems' The Powder may be P to the toxicant solution and dried. The sections were then ina dry f Preferably a Suspenslon, m 'r j fested with cabbage looper Ian/2m Munality readings cal carriersmclude fuller s earth, kaolm clays, silicas, were taken after 24 hours and other highly absorbent, readily wettable, mogranic American Cockroach (Periplanera americana L.): A diluems' f i wetting dispersing 9 emulsifying 500 ppm acetone Solution of the candidate toxicant agents used in agricultural formulations include, for exwas placed in a microsprayer (atomizer). A random l5 ample: the alkyl and alkylaryl sulfonates and their somixture of anesthetized male and female roaches was dlum Saltsi, alkylamlde sulfonates' mcludmg fatty placed in a container and 55 mg of the above-described methyl taundes; alkylaryl, poll/ether alcohols sulfated acetone solution was sprayed on it. A lid was placed on alcohols i polyvinyl alcohols; piJlethylene the c0mainer A mortality reading was made after 24 Ides, sulfonated animal and vegetable oils; sulfonated hours petroleum oils; fatty acid esters of polyhydric alcohols Housefly (Musm domestic, L. )I A 500 ppm acetone and the ethylene ox|de addition productsof such esters; solution of the candidate toxicant was placed in a miand the products of long-chain mercapmns crosprayer (atomizer). A random mixture of anestheethylene oxlde' M olher types of useful surface active agents are available in commerce. The surfacetized male and female flies was placed in a container active agent, when used, normally comprises from 1% and 55 mg of the above-described acetone solution was to 15% b Wei ht of the esficidal Com osmon sprayed on it. A lid was placed on the container. A y g p p mortality reading was made after 24 hours. Dusts are freely flowing admixtures of the active in- Two-Spotted Mite (Telramuchus urticae): An ace gredient with finely divided solids such as talc, natural tone solution of the candidate toxicant containing a l y se gl pyrophyllite. Chalk. diatomaceous small amount of monionic emulsifier diluted with water earths. Calcium ph phates, Ca c um and magnesium to 40 ppm. Pinto-bean leaves hi h were infe ted i h carbonates, sulfur, lime, flours, and other organic and mites were dipped in the toxicant solution. Mortality inorganic Solids which act as dispersant-5 and Carriers eadin were tak ft r 24 h0u|'5 for the toxicant. These finely divided solids have an av- Aphis (Aphis gossypii Glover): An acetone solution of erage particule size of less that about 50 microns. A th did r toxicant containing a n amount f typical dust formulation useful herein contains 75% silnonionic emulsifier was diluted with water to ppm. R33 and 25% f e o icant- C cumber leaves inf st d with th cotton hi were Useful liquid concentrates include the emulsifiable dipped in the toxicant solution. Mortality readings were concentrates, which are homogeneous liquid or paste then taken after 24 hours. 40 compositions which are readily dispersed in water or TABLE III MORTALITY CABBAGE AMERICAN MITE Ex. LOOPER COCKROACH HOUSEFLY 100 APHIS No. (500 ppm) (500 ppm) (500 ppm) ppm) (40 ppm) 1 0 I00 I00 l5 l5 2 lOO I00 I00 0 70 5 I00 100 I00 96 9s 6 so 100 I00 100 94 The compounds of this invention are toxic to a variother dispersant, and may consist entirely of the toxiety of crop and household pests, in addition to the typicant with a liquid or solid emulsifying agent, or may cal pests exemplified above. As most agricultural also contain a liquid carrier, such as xylene, heavy arochemicals, they are not usually applied full-strength, matic naphthas, isophorone, and other nonvolatile orbut are generally incorporated with conventional bioganic solvents. For application, these concentrates are logically inert extenders or carriers normally employed dispersed in water or other liquid carrier, and are norfor facilitating dispersion of active ingredients for agrimally applied as a spray to the area to be treated. cultural chemical applications, recognizing the ac- Other useful formulations for insecticidal applicaeepted f h t the formulation and mode of applications include simple solutions of the active ingredient tion may effect the activity ofa material. The toxicants in a dispersant in which it is completely soluble at the of this invention may be applied as Sprays, dusts Or desired concentration,such as acetone, alkylated naphgranules to the insects or their environment or to hosts susceptible to insect attack. They may be formulated as granules of large particle size, as powdery dusts, as wetthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover-crop canopy. Baits, prepared by mixing solid or liquid concentrates of the toxicant with a suitable food. such as a mixture of cornmeal and sugar. are useful formulations for control of insect pests. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier. such as the Freons, may also be used. All of these techniques for formulating and applying the active ingredient are well known in the art.

The percentages by weight of the toxicant may vary according to the manner in which the composition is to be applied and the particular type of formulation. but in general comprise 0.5 to 95% of the toxicant by weight of the pesticidal composition.

The pesticidal compositions may be formulated and applied with other active ingredients, including other nematocides, insecticides. fungicides. bactericides. plant growth regulators, fertilizers. etc. In applying the chemical. an insecticidally effective amount and concentration of the toxicants of this invention are. of course. employed.

wherein R and R individually are alkyl of l to 6 carbon atoms or alkenyl of 3 to 6 carbon atoms; R is hydrogen. alkyl of l to 6 carbon atoms or haloalkyl of l to 6 carbons atoms and l to 3 fluorine, chlorine or bromine; R and R individually are hydrogen or alkyl of 1 to 6 carbon atoms; R is alkyl of l to 6 carbon atoms. haloalkyl of 1 to 6 carbon atoms and l to 3 fluorine. chlorine or bromine. phenyl or phenyl substituted with 1 to 2 alkyl of l to 4 carbon atoms. fluorine, chlorine or bromine. with the proviso that two alkyl R and R groups may be joined to form a 5 or 6-membered carbocyclic ring.

2. The compound of claim I wherein R is hydrogen.

3. The compound of claim 2 wherein R is alkyl of l to 6 carbon atoms. R is alkyl of l to 6 carbon atoms. R is alkyl of l to 6 carbon atoms and R is hydrogen.

4. The compound of claim 3 wherein R" is alkyl of l to 6 carbon atoms.

5. The compound of claim 4 wherein R. R R and R are methyl.

6. The compound of claim 3 wherein R and R are joined to form a 5- or 6-membered carbocyclic ring.

7. The compound of claim 6 wherein R and R are joined to form a dimethylene or trimethylene group.

8. The compound of claim 7 wherein R and R are methyl and R and R are joined to form a trimethylene group.

9. The compound of claim 3 wherein R is phenyl or phenyl substituted with l to 2 alkyl of l to 4 carbon atoms, fluorine. chlorine or bromine.

10. The compound of claim 9 wherein R. R and R are methyl and R is phenyl. 

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1 wherein R3 is hydrogen.
 3. The compound of claim 2 wherein R1 is alkyl of 1 to 6 carbon atoms, R2 is alkyl of 1 to 6 carbon atoms, R4 is alkyl of 1 to 6 carbon atoms and R5 is hydrogen.
 4. The compound of claim 3 wherein R6 is alkyl of 1 to 6 carbon atoms.
 5. The compound of claim 4 wherein R1, R2, R4 and R6 are methyl.
 6. The compound of claim 3 wherein R4 and R6 are joined to form a 5- or 6-membered carbocyclic ring.
 7. The compound of claim 6 wherein R4 and R6 are joined to form a dimethylene or trimethylene group.
 8. The compound of claim 7 wherein R1 and R2 are methyl and R4 and R6 are joined to form a trimethylene group.
 9. The compound of claim 3 wherein R6 is phenyl or phenyl substituted with 1 to 2 alkyl of 1 to 4 carbon atoms, fluorine, chlorine or bromine.
 10. The compound of claim 9 wherein R1, R2 and R4 are methyl and R6 is phenyl. 